EP2776819B1 - Capteur de gaz électrochimique utilisant un liquide ionique comme électrolyte pour la détection de l'ammoniac et d'amines - Google Patents
Capteur de gaz électrochimique utilisant un liquide ionique comme électrolyte pour la détection de l'ammoniac et d'amines Download PDFInfo
- Publication number
- EP2776819B1 EP2776819B1 EP12783553.6A EP12783553A EP2776819B1 EP 2776819 B1 EP2776819 B1 EP 2776819B1 EP 12783553 A EP12783553 A EP 12783553A EP 2776819 B1 EP2776819 B1 EP 2776819B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- ammonia
- gas sensor
- ionic liquid
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims description 86
- 239000002608 ionic liquid Substances 0.000 title claims description 52
- 239000003792 electrolyte Substances 0.000 title claims description 44
- 229910021529 ammonia Inorganic materials 0.000 title claims description 37
- 150000001412 amines Chemical class 0.000 title claims description 25
- 238000001514 detection method Methods 0.000 title description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000654 additive Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 239000006259 organic additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- CNWONESORNTVSL-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;2,2,2-trifluoroacetate Chemical compound OCC[NH2+]CCO.[O-]C(=O)C(F)(F)F CNWONESORNTVSL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 2
- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- 238000000034 method Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 60
- 238000005259 measurement Methods 0.000 description 32
- -1 antimonate Chemical class 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 15
- 150000001768 cations Chemical class 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- AHRQMWOXLCFNAV-UHFFFAOYSA-O ethylammonium nitrate Chemical compound CC[NH3+].[O-][N+]([O-])=O AHRQMWOXLCFNAV-UHFFFAOYSA-O 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 230000005595 deprotonation Effects 0.000 description 3
- 238000010537 deprotonation reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000012458 free base Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010669 acid-base reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012476 oxidizable substance Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- YCNIBOIOWCTRCL-UHFFFAOYSA-N azane;2,2,2-trifluoroacetic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)F YCNIBOIOWCTRCL-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000010505 homolytic fission reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
- G01N27/4045—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors for gases other than oxygen
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0054—Ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- the present invention relates to an electrochemical gas sensor.
- Such gas sensors generally include at least two electrodes, in the form of one working electrode and one counter electrode. These electrodes find themselves in mutual contact via a conductor or electrolyte.
- Such types of gas sensors and gas cells typically involve one side being open to ambient, e.g., by way of a porous membrane. Gas can flow through such a membrane to the electrodes to be electrochemically converted there. The current resulting from the electrochemical reaction ends up being proportional to the quantity of gas.
- Various arrangements, represented by sulfuric acid or other aqueous electrolytes, have previously been employed as ionic conductors or electrolytes in such gas sensors.
- Ionic liquids have proven to be unique solvents showing solubility, miscibility and other physiochemical properties (e.g., non-volatile properties) over a broad range.
- Ionic liquids are, per definition, liquid salts with a melting point under 100°C.
- the salt structure of ionic liquids requires a correspondingly negligible vapor pressure.
- Many ionic liquids are very stable chemically and electrochemically, and feature high conductivity.
- other ionic liquids show water absorption similarly to an aqueous salt solution. In contrast to aqueous salt solutions, however, these ionic liquids still show an electrical conductivity even at extremely low humidities, while, because of water evaporation, this is not the case for aqueous salts such as LiCl solutions.
- ionic liquids were used based on given cation classes in combination with halide, sulfate, sulfonate, borate, phosphate, antimonate, amide, imide anions.
- Typical cations are substituted imidazolium ions, pyridinium ions, pyrrolidinium ions, phosphonium ions, ammonium ions and guanidinium ions ( DE 10 2005 020 719 B3 ).
- Electrochemical sensors for the detection of ammonia are typically based upon direct oxidation of the gaseous ammonia in the context of molecular nitrogen formation and electron release. However, such sensors exhibit reduced stability, which especially is brought about by exposing the sensor to the ammonia gas for longer time periods.
- the one step that determines reaction speed here is the introduction of equilibrium between electrolyte and gas space.
- this type of measurement system also has the disadvantage of a relatively long response time with the type of ammonia sensor at hand.
- a different measurement principle is embraced in DE 38 41 622 C2 , whereby the provision of gas sensors for ammonia with relatively short response times is facilitated.
- DE 38 41 622 C2 a soluble, non-oxidizable substance is added to the electrolyte, which undergoes a reaction with ammonia during formation of an oxidizable product.
- this oxidizable product can be converted into chemically and electrochemically inert byproducts via electrochemical oxidation.
- Tris (hydroxymethyl) aminomethanhydrochlorid (Tris-HCl) has proven to be especially suitable for this purpose.
- a disadvantage with the described measurement system for ammonia is that the Tris-HCl being used is introduced into a liquid electrolyte.
- the use of aqueous electrolytes does provide a hindrance to the miniaturization of gas sensors as well as performance limitations at low humidity conditions.
- the invention provides an electrochemical gas sensor for detecting a target gas taken from the group consisting of ammonia and amines; comprising: an electrolyte comprising an ionic liquid; further comprising at least two electrodes in electrical contact with said electrolyte and in electrical isolation from each other; characterized in that said ionic liquid is di(2-hydroxyethyl) ammonium trifluooracetate.
- a reference numeral is advanced by a multiple of 10 in indicating a substantially similar or analogous component or element with respect to at least one component or element found in at least one earlier figure among FIGS. 2-4 .
- an electrochemical gas sensor for measuring ammonia and amines, that shows high stability even in the presence of high gas concentrations and that is suitable for miniaturization. Accordingly, an electrochemical gas sensor is availed for the detection of ammonia and amines with an ionic liquid as an electrolyte.
- the ionic liquid that is employed includes at least one protic ammonium cation with at least one dissociable, i.e., separable hydrogen atom, wherein at least one ammonium cation reacts, via deprotonation, with the ammonia and amines to be measured.
- dissociable within the context of the present invention relates to a heterolytical dissociation, i.e the reversible decomposition into a cation and anion. Homolytic cleavages providing radicals do not fall under this definition.
- ammonium cation of the ionic liquid used in a gas sensor so reacts with ammonia and/or amines via the following general equation (as an example): NH 3 + cation of the ionic liquid (HA) ⁇ NH 4 + + deprotonated cation of the ionic liquid (A - )
- the fundamental property of the ionic liquid used in a gas sensor is the capability of the corresponding cation of the ionic liquid to react with the target gas, such as ammonia, in an acid-base reaction.
- the protic ammonium cation applied in the present invention is not based or part of an electron conjugated system.
- Ammonium cations based on alkylated amines having no functional substituents such as ethylammonium cation (with a pKa value of 10.8) are not favourable for the present invention since these cations are not easily deprotonated by the target gas and are thus not able to release a proton in presence of ammonia or amines in a desired manner.
- the free bases of the cation arising from deprotonation with ammonia, can be oxidized at the measurement electrode of the gas sensor.
- the oxidation of this free base as opposed to a direct oxidation of ammonia, provides reduced deviation and drift of the sensor signal, since diverse products are formed in this reaction.
- the oxidation of the free base of the cation of the ionic liquid might occur at a lower potential, thereby permitting a concerted the use of less active catalysts, thus increasing the selectivity of the sensor.
- ammonium cation of the ionic liquid reacts directly, that is, in a direct fashion without an intermediary reactant with the ammonia and/or amines and via deprotonation.
- reaction between the ammonium cation of the ionic liquid and the ammonia and/or amines to be measured not to be direct, but to be carried out via a mediator.
- mediator works in the manner of an intermediary reactant between ammonium cation and ammonia/amine.
- water can be considered as an intermediary reactant, or mediator. At a high ambient humidity, it is absorbed by the ionic liquid. Depending on the nature af the ionic liquid, it might take up significant amounts of water. In the presence of ammonia, water reacts in accordance with this equation: NH 3 + H 2 O ⁇ OH - + NH 4 + In turn, the hydroxide ions so formed react with the ammonium cation of the ionic liquid in accordance with this equation: OH - + cation of ionic liquid (HA) ⁇ H 2 O + deprotonated cation of ionic liquid (A - ) Subsequently, the free base of the cation of the ionic liquid is oxidized at the measurement electrode of the gas sensor, e.g., as described hereabove.
- the type of possible mediator and its concentration, as well as other external conditions depends on whether a direct reaction between an ammonium cation of the ionic liquid and ammonia is being addressed or if mediators are to serve a purpose.
- a gas sensor in accordance with at least one embodiment of the invention is also be used for measuring amines, particularly gaseous amines such as methylamine or ethylamine.
- the ionic liquids used in an electrochemical gas sensor include: di(2-hydroxyethyl) ammonium trifluoroacetate.
- mixtures of different ionic liquids it is also possible to employ mixtures of different ionic liquids.
- a mixture of different ionic liquids is then advantageous if different polarities are to be accommodated in the electrolyte and if, for instance, certain additives need to be released or the water absorption of the electrolyte needs to be controlled.
- the ionic liquid used as an electrolyte can be absorbed in a solid the form of a powder and/or fibrous solid based on silicon dioxide, or not be absorbed in a solid. If the electrolyte is absorbed in a powder and/or interwoven fibrous solid based on silicon dioxide, then a solid-state electrolyte comes to be formed in the gas sensor. In such a solid-state electrolyte, the electrodes of the gas sensor are preferably applied to a gas permeable membrane or, in the powder form, are mixed directly with the electrolyte.
- the powdered solid based on silicon dioxide is a silicate with an average particle size of at least 5 ⁇ m, preferably at least 50 ⁇ m, particularly preferably at least 75 ⁇ m.
- the solid based on silicon dioxide preferably has a specific surface area of at least 50 m 2 /g, preferably at least 100 m 2 /g, most preferably at least 150 m 2 /g, and has a silicon dioxide content of at least 95 wt%.
- a pure silicon dioxide or aluminum or calcium silicate is used for the solid at hand.
- the electrochemical gas sensor includes at least two electrodes that are in electrical contact with the ionic liquid and are electrically isolated from each other. This can be brought about, for instance, by suitable separation elements or by an adequate separation distance. Two-electrode arrangements, that is, a working electrode and a counter electrode, or three-electrode arrangements, that is, a working electrode, a counter electrode and a reference electrode, are preferably employed. Generally, it is also possible to use additional electrodes, such as a cover or protective electrode or more measurement electrodes in the form of a multi-electrode system.
- the electrodes are preferably formed from a metal from the group comprising: Cu, Ni, Ti, Pt, Ir, Au, Pd, Ag, Ru, and Rh, their mixtures, and/or their oxides or carbons (e.g., in the form of carbon nanotubes, graphene, diamond-like carbon or graphite), whereby the electrodes can be formed from the same or different materials.
- the electrodes can each take on an appropriate structure for the sensor construction employed.
- organic and/or metal-organic and/or inorganic additives or additive portions are added to the ionic liquid used as an electrolyte.
- Said additive portions are present in an amount between about 0.05 and about 1 wt%.
- These additives particularly serve to improve the sensitivity, selectivity and robustness of the sensors.
- the additives can be included at 0.05 to 1.5 wt% for organic additives, at 1 to 12 wt% for inorganic additives and at 0.05 to 1 wt% for metal-organic additives.
- the organic additives of the ionic liquid are preferably selected from a group comprising: imidazole, pyridine, pyrrole, pyrazole, pyrimidine, guanine, unsubstituted or substituted with at least one C1-C4 alkyl group, uric acid, benzoic acid and porphyrins and their derivatives.
- a derivative within the meaning of the present invention is compound having a similiar structure derived from a corresponding basic compound. Derivatives are usually compounds in which H-atoms or other groups are replaced by another atom or atom group or in which one or multiple atoms or atom groups are removed.
- the metal-organic additives are preferably selected from a group comprising: metal-organic phthalocyanines and their derivatives, whereby the metal cation of the phthalocyanine is preferably Mn 2+ , Cu 2+ , Fe 2+ , Fe 3+ or Pb 2+ .
- the inorganic additives are preferably selected from a group comprising: alkali halides and ammonium halides, which are unsubstituted or substituted by C1-C4 alkyl, as well as transition metal salts from the group Mn 2+ , Mn 3+ , Cu 2+ , Ag + , Cr 3+ , Cr 6+ , Fe 2+ , Fe 3+ , and lead salts.
- the inorganic additives are selected from this group: lithium bromide, lithium iodide, ammonium iodide, tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrabutylammonium bromide, manganese (II) chloride, manganese (II) sulfate, manganese (II) nitrate, chromium (III) chloride, alkali chromate, iron (II) chloride, iron (III) chloride and lead (II) nitrate.
- the additives discussed above may also be used in mixtures.
- This can encompass mixtures of different additives in the same group, for instance mixtures of various organic additives, as well as mixtures of different additives, for instance mixtures of, e.g., of organic and inorganic additives.
- mixtures of different additives it is possible to customize the sensitivity of the sensors towards specific requirements.
- a gas sensor for the detection of ammonia and amines functions as a second-order head in the classical sense of a Clark cell with precious metal catalysts and carbon used as the measurement and counter electrodes in a two-electrode system, or with an additional electrode in a three-electrode operation.
- the operation of such a gas sensor is thus amperometric, while modes of operation or working other than amperometric are generally possible.
- an ionic liquid can end up being absorbed by a solid based on silicon dioxide.
- the solid appears in the sensor as a filling or layering, or is in pressed form.
- a filling or layering permits a very flexible design of the sensors. Pressing the solid into pellet form is also possible.
- the electrochemical gas sensor is used for amperometric measurements.
- This relates particularly to a gas sensor with an unabsorbed arrangement of ionic fluids with and without additives, and the variant of a solid state electrolyte with ionic liquids (with or without additives).
- FIG. 2 shows a gas sensor 1 that includes a sensor housing 2, within which are disposed a measurement electrode 3, a working electrode 5 and a counter electrode 6.
- the measurement electrode 3 is in communication with ambient via a gas-permeable membrane.
- the electrodes are separated from one another by a separator 4, which is formed from glass fibers or silica structures and is saturated with electrolyte.
- the electrolyte is an ionic liquid containing a protic ammonium cation.
- a compensating volume 7 is afforded, where water can be accommodated during atmospheric humidity fluctuations.
- the sensor is connected to measurement electronics 8, which amplify the sensor current into a measurement signal in the presence of the target gas, in this case ammonia or amines.
- FIG. 3 shows a gas sensor 11 that includes a sensor housing 12, within which are disposed a measurement electrode 13a, working electrode 15 and counter electrode 16.
- the measurement electrode 13a is in communication with the atmosphere via a gas permeable membrane 13.
- the measurement electrode 13a is comprised of a layer with catalyzer/electrode material and electrolyte.
- the electrolyte is embodied by ionic fluid with at least one protic ammonium cation which is capable of reacting with the ammonia or amines to be measured.
- the ionic liquid can be absorbed by a powdered solid based on silicon dioxide.
- the individual electrodes are separated from one another via a separator 14, itself formed from glass fibers or silica structures.
- the working electrode 15 and counter electrode 16 are each positioned adjacent one another at the side of the measurement electrode 13a opposite the separator 14.
- a compensating volume 17 for accommodating water during atmospheric humidity fluctuations.
- the sensor is connected to measurement electronics 18 which, on the one hand, provides a stable and adjustable potential at the working electrode and, on the other hand, provides output information to other devices.
- FIG. 4 shows a gas sensor 21 that includes a sensor housing 22, within which are disposed a measurement electrode 23a, working electrode 25 and counter electrode 26.
- the measurement electrode 23a is in communication with the environmental atmosphere via a gas permeable membrane 23.
- the measurement electrode 23a is comprised of a layer with catalyzer/electrode material and electrolyte.
- the electrolyte is the ionic fluid containing at least one protic ammonium cation according to the present invention, which is absorbed by a powdered solid based on silicon dioxide.
- the measurement electrode 23a and working electrode 25 are in ionic condictive contact with one another via a first separator 24a formed from glass fibers or silica structures that is saturated with ionic electrolytes according to the invention. Further, the working electrode 25 and counter electrode 26 are in ionic condictive contact via a second separator 24b. The counter electrode 26 is thereby positioned at that side of the second separator 24b which is away from or opposite the working electrode 25. In other words, in the present embodiment of a gas sensor, the measurement electrode 23a, working electrode 25 and counter electrode 26 are positioned in a stack. In a rear space of the sensor, a compensating volume 27 serves to accommodate water during atmospheric humidity fluctuations. The sensor is again connected to measurement electronics 28.
- a gas sensor is used with a structure analogous to that of the embodiment of FIG. 2 .
- the sensor used in the present example comprises a measurement electrode, a counter electrode and working electrode, in which each electrode included iridium. Electrolyte-saturated separators are positioned between the electrodes to ensure ionic conductivity between the individual electrodes and to prevent short circuiting between the electrodes.
- signal stability increases when DHEA-TFH (containing a protic ammonium cation of the present invention) is used, as compared to the aqueous lithium chloride electrolyte solution and also to the ionic liquid ethylammonium nitrate (which itself already offers an increase in stability of an ammonia gas sensor).
- the stability of the ammonia gas sensor enhanced with the ionic liquid DHEA-TFA has a pKa value of 8.88, while that of the ionic liquid ethylammonium nitrate is 10.81. Since the stability of the gas sensor using DHEA-TFH as compared to that with ethylammonium nitrate is significantly increased (see FIG. 5 ), the impact and importance of the pKa value of the ionic liquid is apparent.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Claims (4)
- Capteur électrochimique de gaz (1, 11) destiné à détecter un gaz cible pris dans le groupe constitué par l'ammoniac et les aminés ; comprenant :un électrolyte comprenant un liquide ionique ;comprenant en outre au moins deux électrodes (5, 6 ; 15, 16) en contact électrique avec ledit électrolyte et en isolation électrique l'une de l'autre ;caractérisé en ce queledit liquide ionique est le trifluoroacétate de di(2-hydroxyéthyl)ammonium.
- Capteur de gaz selon la revendication 1, dans lequel ledit électrolyte est absorbé dans un solide, de préférence un solide choisi dans le groupe constitué par : un solide à base de SiO2 sous forme de poudre ; et un solide à base de SiO2 sous forme de fibres.
- Capteur de gaz selon la revendication 1, dans lequel ledit électrolyte comprend en outre une partie additifs comprenant au moins un additif choisi dans le groupe constitué par : les additifs organiques ; les additifs métallo-organiques ; et les additifs inorganiques.
- Procédé de détection d'un gaz cible, en particulier d'ammoniac et d'amines, au moyen d'un capteur de gaz (1 ; 11) selon au moins une des revendications précédentes.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102011085174A DE102011085174A1 (de) | 2011-10-25 | 2011-10-25 | Elektrochemischer Gassensor mit einer ionischen Flüssigkeitals Elektrolyt zum Nachweis von Ammoniak und Aminen |
DE102011087592A DE102011087592A1 (de) | 2011-12-01 | 2011-12-01 | Elektrochemischer Gassensor mit einer ionischen Flüssigkeit als Elektrolyt zum Nachweis von Ammoniak und Aminen |
PCT/EP2012/071141 WO2013060773A1 (fr) | 2011-10-25 | 2012-10-25 | Capteur de gaz électrochimique utilisant un liquide ionique comme électrolyte pour la détection de l'ammoniac et d'amines |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2776819A1 EP2776819A1 (fr) | 2014-09-17 |
EP2776819B1 true EP2776819B1 (fr) | 2018-12-19 |
Family
ID=47146357
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12783553.6A Active EP2776819B1 (fr) | 2011-10-25 | 2012-10-25 | Capteur de gaz électrochimique utilisant un liquide ionique comme électrolyte pour la détection de l'ammoniac et d'amines |
Country Status (9)
Country | Link |
---|---|
US (1) | US9395323B2 (fr) |
EP (1) | EP2776819B1 (fr) |
JP (1) | JP6131261B2 (fr) |
KR (1) | KR20140098083A (fr) |
CN (1) | CN103890577B (fr) |
AU (1) | AU2012330453B2 (fr) |
CA (1) | CA2853374C (fr) |
RU (1) | RU2617845C2 (fr) |
WO (1) | WO2013060773A1 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2776819B1 (fr) | 2011-10-25 | 2018-12-19 | MSA Europe GmbH | Capteur de gaz électrochimique utilisant un liquide ionique comme électrolyte pour la détection de l'ammoniac et d'amines |
DE102013014994A1 (de) * | 2013-09-09 | 2015-03-12 | Dräger Safety AG & Co. KGaA | Elektrochemischer Gassensor, flüssiger Elektrolyt und Verwendung eines flüssigen Elektrolyten in einem elektrochemischen Gassensor |
DE102014003316B4 (de) * | 2013-11-21 | 2019-07-25 | Dräger Safety AG & Co. KGaA | Elektrochemischer Sensor |
DE102014007137A1 (de) * | 2014-05-16 | 2015-11-19 | Dräger Safety AG & Co. KGaA | Elektrode für einen elektronischen Gassensor, Herstellungsverfahren für eine Elektrode und Verwendung einer Elektrode |
EP3115774B1 (fr) | 2015-07-06 | 2020-05-06 | Stichting IMEC Nederland | Détecteur de gaz avec mesure de fréquence de l'impédance |
DE102015012440B4 (de) | 2015-09-28 | 2020-02-13 | Dräger Safety AG & Co. KGaA | Elektrochemischer Gasgenerator für Ammoniak unter Verwendung lonischer Flüssigkeiten und Verwendung des Gasgenerators |
JP6694645B2 (ja) * | 2016-03-01 | 2020-05-20 | 国立研究開発法人産業技術総合研究所 | 塩基性ガス吸収剤及び塩基性ガス分離回収方法 |
JP7391540B2 (ja) * | 2019-05-31 | 2023-12-05 | 浜松ホトニクス株式会社 | 匂いセンサ及び匂い検出方法 |
CN115711928A (zh) * | 2022-11-09 | 2023-02-24 | 郑州炜盛电子科技有限公司 | 柔性电解质及其制备方法与应用 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3841622A1 (de) * | 1988-12-10 | 1990-06-13 | Draegerwerk Ag | Elektrochemische messzelle zur amperometrischen bestimmung von ammoniak und dessen derivate |
US6248224B1 (en) | 1999-05-12 | 2001-06-19 | Mst Analytics Inc. | Toxic sensor and method of manufacture |
RU25226U1 (ru) * | 2002-01-23 | 2002-09-20 | Общество с ограниченной ответственностью "ВЗОР" | Электрохимический датчик |
US7060169B2 (en) | 2002-08-14 | 2006-06-13 | Mst Technology Gmbh | Electrochemical cell for gas sensor |
GB0407908D0 (en) | 2004-04-07 | 2004-05-12 | Univ York | Ionic liquids |
US8697309B2 (en) * | 2004-09-03 | 2014-04-15 | Nissan Motor Co., Ltd. | Proton conductor and fuel cell using the same |
JP4597622B2 (ja) * | 2004-09-27 | 2010-12-15 | 根本特殊化学株式会社 | 電気化学式ガスセンサ |
DE102005020719B3 (de) | 2005-05-04 | 2006-09-14 | Drägerwerk AG | Offner elektrochemischer Sensor |
JP2008064578A (ja) * | 2006-09-06 | 2008-03-21 | Horiba Ltd | イオン液体特性測定方法 |
GB0704972D0 (en) | 2007-03-15 | 2007-04-25 | Varney Mark S | Neoteric room temperature ionic liquid gas sensor |
DE102008044238A1 (de) | 2008-12-01 | 2010-06-10 | Msa Auer Gmbh | Elektrochemischer Gassensor mit einer ionischen Flüssigkeit als Elektrolyt, welche organische und/oder metallorganische und/oder anorganische Zusätze aufweist |
EP2370808B2 (fr) | 2008-12-01 | 2020-07-22 | MSA Europe GmbH | Capteurs de gaz électrochimiques à systèmes d'électrolyte liquide ionique |
DE102008044240B4 (de) | 2008-12-01 | 2013-12-05 | Msa Auer Gmbh | Elektrochemischer Gassensor mit einer ionischen Flüssigkeit als Elektrolyt, welche mindestens ein Mono-, Di- oder Trialkylammonium-Kation enthält |
DE102008044239A1 (de) | 2008-12-01 | 2010-06-10 | Msa Auer Gmbh | Elektrochemischer Gassensor mit einer in einem Feststoff auf SiO2-Basis absorbierten ionischen Flüssigkeit als Elektrolyt mit organischen und/oder metallorganischen und/oder anorganischen Zusätzen |
DE102010063626A1 (de) | 2010-12-21 | 2012-06-21 | Henkel Ag & Co. Kgaa | Geschirrspülmittelkompaktate |
EP2776819B1 (fr) | 2011-10-25 | 2018-12-19 | MSA Europe GmbH | Capteur de gaz électrochimique utilisant un liquide ionique comme électrolyte pour la détection de l'ammoniac et d'amines |
-
2012
- 2012-10-25 EP EP12783553.6A patent/EP2776819B1/fr active Active
- 2012-10-25 RU RU2014120795A patent/RU2617845C2/ru active
- 2012-10-25 AU AU2012330453A patent/AU2012330453B2/en active Active
- 2012-10-25 KR KR20147013382A patent/KR20140098083A/ko not_active Application Discontinuation
- 2012-10-25 WO PCT/EP2012/071141 patent/WO2013060773A1/fr active Application Filing
- 2012-10-25 US US14/354,011 patent/US9395323B2/en active Active
- 2012-10-25 CN CN201280052362.4A patent/CN103890577B/zh active Active
- 2012-10-25 JP JP2014537610A patent/JP6131261B2/ja active Active
- 2012-10-25 CA CA2853374A patent/CA2853374C/fr active Active
Non-Patent Citations (1)
Title |
---|
CHUAN ZHAO ET AL: "Electrochemistry of Room Temperature Protic Ionic Liquids", JOURNAL OF PHYSICAL CHEMISTRY PART B: CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL, vol. 112, no. 23, 1 June 2008 (2008-06-01), US, pages 6923 - 6936, XP055439464, ISSN: 1520-6106, DOI: 10.1021/jp711804j * |
Also Published As
Publication number | Publication date |
---|---|
RU2617845C2 (ru) | 2017-04-28 |
JP2014531036A (ja) | 2014-11-20 |
JP6131261B2 (ja) | 2017-05-17 |
CN103890577A (zh) | 2014-06-25 |
WO2013060773A1 (fr) | 2013-05-02 |
US9395323B2 (en) | 2016-07-19 |
AU2012330453B2 (en) | 2015-08-06 |
CA2853374C (fr) | 2020-02-25 |
CN103890577B (zh) | 2016-08-24 |
CA2853374A1 (fr) | 2013-05-02 |
RU2014120795A (ru) | 2015-12-10 |
AU2012330453A1 (en) | 2014-05-15 |
KR20140098083A (ko) | 2014-08-07 |
US20140299470A1 (en) | 2014-10-09 |
EP2776819A1 (fr) | 2014-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2776819B1 (fr) | Capteur de gaz électrochimique utilisant un liquide ionique comme électrolyte pour la détection de l'ammoniac et d'amines | |
US9945806B2 (en) | Electrochemical gas sensors with ionic liquid electrolyte systems | |
KR101671407B1 (ko) | 하나 이상의 모노알킬암모늄 양이온, 디알킬암모늄 양이온 또는 트리알킬암모늄 양이온을 포함하는 이온성 액체 전해질 시스템을 구비한 전기화학적 가스 센서 | |
DE102011087592A1 (de) | Elektrochemischer Gassensor mit einer ionischen Flüssigkeit als Elektrolyt zum Nachweis von Ammoniak und Aminen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20140521 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: WARRATZ, RALF |
|
DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: MSA EUROPE GMBH |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20170410 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602012054907 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: G01N0027404000 Ipc: G01N0033000000 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: G01N 33/00 20060101AFI20180615BHEP Ipc: G01N 27/404 20060101ALI20180615BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20180727 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602012054907 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1079259 Country of ref document: AT Kind code of ref document: T Effective date: 20190115 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190319 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190319 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1079259 Country of ref document: AT Kind code of ref document: T Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190320 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190419 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190419 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602012054907 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
26N | No opposition filed |
Effective date: 20190920 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191025 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191031 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191031 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20191031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191025 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20121025 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181219 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602012054907 Country of ref document: DE Representative=s name: JONES DAY RECHTSANWAELTE PATENTANWAELTE, DE |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230626 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20230831 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230911 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230830 Year of fee payment: 12 |